JP2014159591A - Method of producing olefin polymer particles - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of efficiently producing olefin polymer particles having an excellent particulate morphology without fouling accompanied.SOLUTION: A solid catalyst (K) for olefin polymerization contains a specific Zr-based metallocene-based compound and simultaneously meets the following requirements [1] and [2]: [1] the loss of ignition is 30 wt.% or less as measured on a differential thermobalance; and [2] after normal-temperature steam treatment and contact with acetonitrile, an eluted component contains a compound having a molecular skeleton of the specified general formula [I], where R is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.

Description

  The present invention relates to a method for producing olefin polymer particles.

  Metallocene compounds known as homogeneous catalysts, such as polyethylene, polypropylene, ethylene / α-olefin copolymers, propylene / α-olefin copolymers, metallocene compounds of Group 4 metals such as zirconium, etc. It is known that it can be produced by polymerizing or copolymerizing an olefin in the presence of a metallocene catalyst containing a cocatalyst component such as an organic aluminum component. As such a metallocene-based catalyst, a “homogeneous catalyst” composed of a metallocene compound and a promoter component such as aluminoxane, and a “supported solid catalyst” in which a metallocene or promoter component is supported on a carrier are known.

  From the viewpoint of the polyolefin industry, homogeneous catalysts can be suitably used for solution polymerization processes, but when used in gas phase polymerization processes and slurry polymerization processes, the polymer becomes amorphous particles and the bulk density is low. There has been a problem that formation and adhesion of lumps occur in the polymerization vessel. On the other hand, it is known that the supported solid catalyst is excellent in the polymer particle shape and the bulk density in the gas phase polymerization process and the slurry polymerization process as compared with the homogeneous catalyst. However, polymer lump, sheet-like polymer, etc. may be generated during polymerization (hereinafter, this phenomenon may be referred to as “fouling”), which hinders long-term and stable polymerization operation. There was a thing.

  When producing a polymer containing a component having a low melting point, for example, an ethylene / propylene copolymer having a relatively high ethylene content, or a polymerization of propylene alone or a mixture of propylene and a small amount of ethylene in the previous stage of the multistage polymerization process is continuously performed. In the production of the so-called propylene / ethylene block copolymer, in which the copolymerization of propylene and ethylene is continuously performed in the subsequent stage to produce an amorphous propylene / ethylene copolymer, fouling occurs particularly. It was known that it was easy, and a solution was sought by the industry.

  As a solution, for example, Japanese Patent Application Laid-Open No. 2000-297114 discloses that a catalyst in which a surfactant is supported on a solid catalyst obtained by prepolymerizing olefin is used for polymerization. Japanese Patent Application Laid-Open No. 2000-327707 discloses a polymerization method in which a surfactant is added during polymerization using a solid catalyst obtained by prepolymerizing an olefin. However, these effects are not sufficient. In addition, when a surfactant is added to the polymerization step, an apparatus for supplying the surfactant to the polymerization facility is required, which is not preferable from the viewpoint of economy.

  On the other hand, a method for washing a metallocene-supported solid catalyst with a solvent is also disclosed. For example, WO00 / 008080 pamphlet discloses a method of washing a metallocene-supported solid catalyst multiple times with a specific solvent at a specific temperature. Japanese Patent Application Laid-Open No. 2004-51715 discloses a method of washing the metallocene-supported solid catalyst until the amount of transition metal derived from the metallocene compound in the washing waste liquid becomes a certain concentration or less. Japanese Patent Laid-Open No. 2002-284808 discloses a method of washing a prepolymerized metallocene-supported solid catalyst with an organic solvent containing organoaluminum.

However, these methods that require highly efficient cleaning require a large amount of solvent and also generate a large amount of waste liquid. Furthermore, it can be said that there are many problems from the viewpoint of industrial production, for example, the cleaning process requires a long time.
JP 2000-297114 A JP 2000-327707 A WO00 / 008080 pamphlet JP 2004-51715 A JP 2002-284808 A Angew. Chem. Int. Ed. Engl., 24, 507 (1985)

  The problem to be solved by the present invention is to provide a solid catalyst for olefin polymerization for efficiently producing an olefin polymer excellent in particle properties without causing fouling and greatly reducing polymerization activity. Another object of the present invention is to provide a method for polymerizing olefins in the presence of the solid catalyst.

  In order to solve the problems of the above-mentioned known techniques, the present inventors have conducted extensive studies, and as a result, by using a solid catalyst for olefin polymerization that satisfies specific requirements, an olefin polymer having excellent particle properties can be obtained. It has been found that it can be efficiently produced without causing fouling.

That is, the solid catalyst for olefin polymerization (K) of the present invention is characterized by satisfying the following requirements [1] and [2] simultaneously.
[1] The loss on ignition measured with a differential thermobalance is 30% by weight or less.
[2] A component having a molecular skeleton represented by the following general formula [I] is contained in the elution component to acetonitrile after contact with water vapor at room temperature and subsequent treatment with acetonitrile.

（上記一般式[Ｉ]において、Ｒは水素原子又は炭素数１〜１２のアルキル基を示す。）

(In the above general formula [I], R represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.)

In a preferred embodiment of the solid catalyst for olefin polymerization (K) of the present invention, the following requirement [3] is satisfied in addition to the requirements [1] and [2].
[3] There must be substantially no non-volatile component dissolved in the filtrate after the solid part has been filtered off after contact with hexane.

  In another aspect of the present invention, the solid catalyst for olefin polymerization (K) is prepolymerized with at least one olefin selected from ethylene and an α-olefin having 3 to 8 carbon atoms. It relates to the solid catalyst (K ′). In the following description, the solid catalyst (K ′) may be abbreviated as “preliminary polymerization catalyst”.

  In the present invention, ethylene and a carbon number of 3 to 12 in the presence of the solid catalyst for olefin polymerization (K) or (K ′) and, if necessary, the (B) group 13 element-containing compound of the periodic table. The present invention relates to a method for polymerizing one or more monomers (M) selected from α-olefins. In this polymerization method, the monomer (M) is propylene and one or more monomers selected from ethylene and an α-olefin having 4 to 10 carbon atoms, or from ethylene and an α-olefin having 3 to 10 carbon atoms. A preferred embodiment is one or more selected monomers.

  The present invention further includes ethylene and a carbon number of 3 to 3 in the presence of the solid catalyst for olefin polymerization (K) or (K ′) and, if necessary, the (B) group 13 element-containing compound of the periodic table. The present invention relates to olefin polymer particles obtained by a method of polymerizing one or more monomers (M) selected from 12 α-olefins.

  One of the preferred embodiments of the olefin polymer particles is that the repeating unit derived from propylene (U1) is a repeating unit of one or more olefins selected from 50 to 100 mol%, ethylene and an α-olefin having 4 to 10 carbon atoms. It is an olefin polymer particle which contains (U2) in the ratio of 0-50 mol%. (The olefin polymer particles may be referred to as “propylene-based polymer particles” in the following description.) Among these, propylene-based polymer particles having a melting point (Tm) of 130 ° C. or less are preferred embodiments. Propylene polymer particles having a bulk density of 0.30 (g / ml) or more are a more preferred embodiment.

  Two preferred embodiments of the olefin polymer particles include a repeating unit (U3) derived from ethylene having a repeating unit (U4) of at least one olefin selected from 50 to 100 mol% and an α-olefin having 3 to 10 carbon atoms. Is an olefin polymer particle containing 0 to 50 mol%. (The olefin polymer particles may be referred to as “ethylene polymer particles” in the following description.)

  Provided are a solid catalyst for efficiently producing an olefin polymer having excellent particle properties without causing fouling, and a method for polymerizing olefins in the presence of the solid catalyst. According to the polymerization method of the present invention, the effects of the present invention can be fully exhibited even in the production of a low-melting-point polymer, which is prone to fouling and difficult to produce efficiently.

The ¹ H-NMR spectrum chart of the elution component to acetonitrile after the contact of the solid catalyst for olefin polymerization obtained in Example 1 and deuterated acetonitrile is shown.

  Hereinafter, the best mode for carrying out the present invention is as follows: (1) a solid catalyst for olefin polymerization, (2) an olefin polymerization method using the catalyst, and (3) polymer particles obtained by the polymerization method. Details will be described in order.

(1) Solid catalyst for olefin polymerization The solid catalyst for olefin polymerization (K) of the present invention simultaneously satisfies the following requirements [1] and [2], and preferably satisfies the requirements [1], [2] and [3] It is characterized by satisfying at the same time.
[1] The loss on ignition measured with a differential thermobalance is 30% by weight or less.
[2] A component having a molecular skeleton represented by the following general formula [I] is contained in an elution component of acetonitrile after contact with normal temperature water vapor and treatment followed by acetonitrile.

(In the above general formula [I], R represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.)
[3] There must be substantially no non-volatile component dissolved in the filtrate after the solid part has been filtered off after contact with hexane.

The requirements [1] to [3] will be described in detail below.
(Requirement [1])
The solid catalyst (K) for olefin polymerization of the present invention is characterized in that the loss on ignition measured with a differential thermal balance is 30% by weight or less, preferably 25% by weight or less, more preferably 20% by weight or less. As will be described later, the loss on ignition related to the present invention uses alumina as a reference material, samples about 10 mg in the air, raises the temperature to 600 ° C. at a rate of 5 ° C./min, and then reaches 30 ° C. at 600 ° C. In the temperature rising profile held for a minute, it is defined as the weight reduction rate (% by weight) at 200 ° C. to 600 ° C., based on the weight at 200 ° C.

  In the present invention, it is preferable that the residue after ignition is substantially composed of atoms selected from aluminum atoms, silicon atoms and oxygen atoms. A more preferred embodiment is an inorganic fine particle containing an oxygen atom as an essential atom and containing one or more atoms selected from an aluminum atom and a silicon atom. The phrase “consisting essentially of atoms selected from aluminum atoms, silicon atoms and oxygen atoms” means that the total amount of atoms selected from aluminum atoms, silicon atoms and oxygen atoms relative to the total amount of the burning residue is based on weight. Is defined as 80% or more.

  The ignition residue relating to the present invention is substantially composed of an atom selected from aluminum atom, silicon atom and oxygen atom. This means that the ignition residue relating to the invention is converted into an element such as inductively coupled plasma analysis (ICP). It can be easily quantified and identified by performing a known analysis such as an analysis method or ion chromatography.

(Requirement [2])
The solid catalyst for olefin polymerization (K) of the present invention is characterized by satisfying not only the requirement [1] but also the following requirement [2].
[2] A component having a molecular skeleton represented by the following general formula [I] is contained in the elution component to acetonitrile after contact with water vapor at room temperature and subsequent treatment with acetonitrile.

That is, the component contained in the elution component of acetonitrile after contact with water vapor at normal temperature and after treatment with acetonitrile has a skeleton represented by the general formula [I]. The skeleton can be identified by a known analysis method such as a nuclear magnetic resonance (NMR) spectrum as described later. (In the following description, the molecular skeleton represented by the general formula [I] may be referred to as an “oxyalkylene skeleton”.)

In the general formula [I], R represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. Examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n- Examples include straight-chain or branched alkyl groups such as hexyl group, n-heptyl group, n-octyl group and n-nonyl group, but when a solid catalyst in which R is a methyl group is used. It is preferable because it is excellent in polymerization activity and fouling suppression effect.

  The treatment with water vapor at room temperature is performed by exposing the olefin polymerization solid catalyst (K) for 5 days or more in a desiccator equipped with a saturated aqueous potassium acetate solution. At this time, in order to sufficiently bring the solid catalyst (K) into contact with the water vapor, the solid catalyst (K) is spread evenly in the container and appropriately stirred and mixed as necessary.

Next, the solid material that has been subjected to the steam treatment by the above method is added to acetonitrile, and the mixture is stirred at 20 to 30 ° C. for 30 minutes to 10 hours. Deuterated acetonitrile can be used instead of acetonitrile. At this time, the weight ratio [(weight of S) / (weight of solid)] between acetonitrile (S) and the solid is preferably 1: 0.15 to 1: 1.
Then, in order to remove a solid part, it filters using a membrane filter, glass wool, etc. There is no particular limitation on the mesh of the filter medium such as a filter unless it interferes with the subsequent NMR analysis of the filtrate.

  The content of the compound having the skeleton represented by the above general formula [I] eluted from the solid catalyst for olefin polymerization (K), calculated from the NMR analysis of the filtrate, is usually the solid catalyst for olefin polymerization (K ) To more than 0.20% by weight and 10% by weight or less, preferably 0.3 to 5% by weight. When the content of the compound having a skeleton represented by the general formula [I] is less than 0.1% by weight, fouling occurs during olefin polymerization, and when the olefin polymer particles are propylene polymer particles, the bulk density When the content exceeds 10% by weight, the polymerization activity may decrease.

The analysis method of the dissolved component is not particularly limited, but when deuterated acetonitrile is used in the above operation, it can be analyzed by ¹ H-NMR (nuclear magnetic resonance spectrum) method. In the general formula [I], a signal derived from a hydrogen atom bonded to a carbon atom adjacent to an oxygen atom is observed at 3 to 4 ppm when tetramethylsilane is used as a reference in deuterated acetonitrile. In the general formula [I], when R is, for example, a methyl group, a signal derived from the methyl group is observed at 0.8 to 1.5 ppm.

The content of the skeleton represented by the general formula [I] can be calculated by adding a reference substance during the ¹ H-NMR measurement described above and measuring the signal intensity ratio. As the reference substance, a substance that does not overlap with the solvent or dissolved component is preferable, and specific examples include benzene, chlorobenzene, naphthalene, chloroform, methylene chloride, and the like.

(Requirement [3])
In a preferred embodiment of the solid catalyst (K) for olefin polymerization of the present invention, in addition to the above requirements [1] and [2], the following requirement [3] is satisfied.
[3] There must be substantially no non-volatile component dissolved in the filtrate after the solid part has been filtered off after contact with hexane.
The contact between the solid catalyst for olefin polymerization (K) and hexane is all carried out in an inert gas atmosphere such as dry nitrogen or dry argon, and hexane is sufficiently dehydrated and deoxygenated.

  In the contact of the solid catalyst for olefin polymerization (K) and hexane, hexane uses 30 to 100 times by weight of the solid catalyst for olefin polymerization (K) and is stirred at 20 to 30 ° C. for 30 minutes to 10 hours. Touch the bottom. Thereafter, filtration is performed using a membrane filter having a pore size large enough to remove the solid part.

  The fact that the non-volatile component dissolved in the filtrate is substantially absent means that the filtrate obtained by the above operation is concentrated under reduced pressure at 20 ° C. to 30 ° C. and further constant at 20 ° C. to 30 ° C. and 1 to 5 hPa. The resulting concentrated and dried product is 5% by weight or less, preferably 3% by weight or less, more preferably 1% by weight or less of the weight of the solid catalyst for olefin polymerization (K) subjected to contact. Particularly preferably, it means 0.5% by weight or less.

  The preparation method of the solid catalyst for olefin polymerization (K) of the present invention is limited as long as the requirements [1] and [2] are satisfied simultaneously, and preferably [1], [2] and [3] are satisfied simultaneously. However, the following method described in detail in the examples of the present application is preferably employed because of its preparation efficiency.

That is, the solid catalyst for olefin polymerization (K) of the present invention can be efficiently prepared by sequentially performing the following steps P1 and P2.
[Step P1] (A) An inorganic fine particle substantially composed of an atom selected from an aluminum atom, a silicon atom and an oxygen atom, and (B) a group 13 element-containing compound of the periodic table in a hydrocarbon medium The process of making it contact.
[Step P2] The suspension obtained in Step P1 above, (C) an oxyalkylene skeleton-containing compound, (D) a metallocene compound, and (B) a group 13 element-containing compound in the periodic table as necessary. The step of contacting in any order.

  Examples of the inorganic fine particles (A) substantially composed of atoms selected from an aluminum atom, a silicon atom and an oxygen atom used in the step P1 include porous oxides, clays and clay minerals.

The porous oxide, specifically SiO _2, Al ₂ O _3, natural or synthetic _{zeolites, SiO 2 -MgO, SiO 2 -Al} 2 O 3, SiO 2 -TiO 2, SiO 2 -V 2 O 5, Examples thereof include porous oxides such as SiO ₂ —Cr ₂ O ₃ and SiO ₂ —TiO ₂ —MgO. Of these, those containing SiO ₂ and / or Al ₂ O ₃ as main components are preferred. Such porous oxides have different properties depending on the type and production method, but the fine particles preferably used in the present invention have a particle size of 1 to 300 μm, more preferably 3 to 100 μm, and a specific surface area of 50 to 50 μm. 1300 m ² / g, more preferably in the range of 200~1200m ² / g, it is desirable that the pore volume is in the range of 0.3~3.0cm ³ / g. Such a carrier is used after being calcined at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary. The particle shape is not particularly limited but is preferably spherical.

  The clay used in the present invention is usually composed mainly of clay minerals. These clays and clay minerals are not limited to natural ones, and artificial synthetic products can also be used. Examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysingelite, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, nacrite, dickite And halloysite. The clay and clay mineral used in the present invention are preferably subjected to chemical treatment. As the chemical treatment, any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the crystal structure of clay can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic matter treatment. Of these, montmorillonite, vermiculite, pectolite, teniolite and synthetic mica are preferred.

  Among these, one or more compounds selected from silica, alumina, and clay minerals are preferably used because they are easily available.

  (B) Periodic Table Group 13 element-containing compounds used in Step P1 can include boron elements and aluminum elements as periodic table Group 13 elements, and these compounds can be used as long as they exhibit Lewis acidity. The form of is not limited at all.

In the present invention, (B) Group 13 element-containing compound of the periodic table is
(b-1) an organoaluminum compound represented by the following general formula [II],

(In the above general formula [II], R ¹ , R ² and R ³ may be the same or different from each other and each represents a group selected from a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms. .)
(b-2) an organoaluminum oxy compound, and
(b-3) organoboron compounds,
It is preferable that it is 1 or more types of compounds chosen from these.

(b-1) As the organoaluminum compound represented by the general formula [II], specifically, trimethylaluminum, triethylaluminum, triisobutylaluminum, diisobutylaluminum hydride, tri-n-butylaluminum, tri-n-hexylaluminum, Examples include tri-n-octylaluminum, ethylaluminum dichloride, diethylaluminum chloride and the like.

  (b-2) The organoaluminum oxy compound may be a conventionally known aluminoxane or a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687.

A conventionally well-known aluminoxane can be manufactured, for example with the following method, and is normally obtained as a solution of a hydrocarbon solvent.
(i) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate, etc. A method of reacting adsorbed water or crystal water with an organoaluminum compound by adding an organoaluminum compound such as trialkylaluminum to the suspension of the hydrocarbon.
(ii) A method of allowing water, ice or water vapor to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, diethyl ether or tetrahydrofuran.
(iii) A method in which an organotin oxide such as dimethyltin oxide or dibutyltin oxide is reacted with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene, or toluene.
(iv) A method of reacting an organoaluminum compound such as trialkylaluminum with a compound having a carboxyl group such as carbon dioxide, benzoic acid or acetic acid in a medium such as benzene, toluene, hexane or decane.

  The aluminoxane may contain a small amount of an organometallic component. Further, after removing the solvent or the unreacted organoaluminum compound from the recovered aluminoxane solution by distillation, it may be redissolved in a solvent or suspended in a poor aluminoxane solvent. Specific examples of the organoaluminum compound used in preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to the above (b-1). Of these, trialkylaluminum is preferred, and trimethylaluminum is particularly preferred. The above organoaluminum compounds are used singly or in combination of two or more.

  The benzene-insoluble organoaluminum oxy compound used in the present invention has an Al component dissolved in benzene at 60 ° C. of usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of aluminum atoms. That is, those which are insoluble or hardly soluble in benzene are preferred.

  These organoaluminum oxy compounds (b-2) are used singly or in combination of two or more.

  Other examples of the organoaluminum oxy compound used in the present invention include modified methylaluminoxane. The modified methylaluminoxane referred to here is an aluminoxane prepared using trimethylaluminum and an alkylaluminum other than trimethylaluminum. Such a compound is generally called MMAO. MMAO can be prepared by the method described in US Pat. No. 4,960,878 and US Pat. MMAO is also commercially produced by Tosoh Finechem Corporation. Such MMAO is an aluminoxane having improved solubility in various solvents and storage stability. Specifically, unlike MMAO, which is insoluble or hardly soluble in benzene, aliphatic hydrocarbons and fatty acids are used. It has the feature of dissolving in cyclic hydrocarbons.

  Furthermore, examples of the organoaluminum oxy compound used in step P1 according to the present invention include an organoaluminum oxy compound containing a boron atom.

  (b-3) Specific examples of the organoboron compound include JP-A-1-501950, JP-A-1-503636, JP-A-3-179005, JP-A-3-179006, and JP-A-3-173. Examples include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in 207703, JP-A-3-207704, WO1996 / 41808, US5321106, and the like. Such boron compounds (b-3) are used singly or in combination of two or more.

  (B) Periodic table group 13 element-containing compound used in step P1 according to the present invention includes (b-1) an organoaluminum compound represented by the above general formula [I] and / or (b- 2) preferably an organoaluminum oxy compound, more preferably (b-1) an organoaluminum compound and (b-2) an organoaluminum oxy compound in combination, (b-1) being triisobutylaluminum, It is particularly preferred that (b-2) is methylaluminoxane. In step P1, when (b-1) an organoaluminum compound and (b-2) an organoaluminum oxy compound are used in combination, the amount used is usually the component (b-1) with respect to the inorganic fine particles (A). 0.5-30 wt%, component (b-2) 10 wt% -200 wt%, preferably (b-1) 3-20 wt%, (b-2) 50 wt% -150 wt% Use.

  The contact method and contact temperature when contacting one or more compounds selected from the component (b-1), the component (b-2) and the component (b-3) in the hydrocarbon medium with the inorganic fine particles (A) are as follows: For example, in the case of using the component (b-1) and the component (b-2), there is a method in which the mixture is usually added individually or individually at −78 ° C. to 100 ° C., and further contact-treated at 0 ° C. to 130 ° C. . Preferably, it adds individually at -10 degreeC-70 degreeC, and makes it contact-process at 50 degreeC-120 degreeC. A hydrocarbon solvent is usually used when the inorganic fine particles (A) and the component (B) are in contact with each other. Preferred hydrocarbon solvents include aromatic hydrocarbons such as toluene, xylene and benzene, saturated hydrocarbons such as hexane, heptane, decane and cyclohexane, ethers such as tetrahydrofuran and diisopropyl ether, and halogenated hydrocarbons such as chloroform and chlorobenzene. Of these, aromatic hydrocarbons such as toluene and xylene, and saturated aliphatic hydrocarbons such as hexane, heptane and decane are preferably used. These solvents are usually used in an amount of 1 to 100 times by weight, preferably 2 to 20 times by weight with respect to the inorganic fine particles (A). Moreover, this solvent may be added independently at the time of a contact, and may be added with the form of the dilution solvent of a component (B).

  Step P2 optionally comprises the suspension obtained in Step P1, (C) an oxyalkylene skeleton-containing compound, (D) a metallocene compound, and (B) a group 13 element-containing compound in the periodic table as necessary. It is the process of making it contact in this order. From the viewpoint of polymerization activity and fouling suppressing ability, a preferred contact order is to contact the suspension obtained in step P1 with the (B) group 13 element-containing compound of the periodic table as necessary, and then ( C) A method in which the oxyalkylene skeleton-containing compound and the (D) metallocene compound are contacted in an arbitrary order, and a more preferable contact order from the same viewpoint as described above is the suspension obtained in step P1, (C This is a method in which an oxyalkylene skeleton-containing compound is brought into contact, and then a mixture of (B) a group 13 element-containing compound in the periodic table and (D) a metallocene compound, which are brought into contact in advance, is added and brought into contact.

  When preparing a solid catalyst for producing propylene polymer particles, it is preferable to use the component (B) in step P2, while a solid catalyst for producing ethylene polymer particles is used. When preparing, use of the said (B) component is not essential in process P2.

  Examples of the (B) group 13 element-containing compound in the periodic table used in step P2 include the same compounds as the group 13B element-containing compound in the periodic table (B) used in step P1. The (B) group 13 element-containing compound used in step P2 is preferably the component (b-1) an organoaluminum compound represented by the general formula [II] alone, and the component (b More preferably, -1) is triisobutylaluminum.

  The (C) oxyalkylene skeleton-containing compound used in Step P2 preferably takes a form in which a hydrogen atom is bonded to the ether oxygen of the oxyalkylene skeleton represented by the general formula [I], and particularly preferably the following general formula A compound having one or two or more skeletons represented by [III], [IV] or [V] in the molecule can be used without limitation.

  In the general formulas [III], [IV] and [V], R represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. Examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n- Examples include straight-chain or branched alkyl groups such as hexyl group, n-heptyl group, n-octyl group, and n-nonyl group, but an oxyalkylene skeleton-containing compound in which R is a methyl group was used. In this case, the polymerization activity and the fouling suppressing effect are excellent, which is preferable. R ′ in the general formula [IV] represents an atom or group similar to R, n is 0 or 1, and the sum of n and m is 2. From the viewpoint of polymerization activity and fouling suppression effect, m is preferably 2.

上記一般式[VI]において、Ｒ^bは、水素原子、炭素数１〜１２のアルキル基であり、Ｒ^aは、水素原子、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基および炭素数１〜２０のアシル基から選ばれる。kは平均繰り返し単位数を表わし、１〜１００の範囲である。このようなポリオキシアルキレン化合物として具体的には、トリエチレングリコール、テトラエチレングリコール、ヘキサエチレングリコール、ヘプタエチレングリコール、ポリエチレングリコール、トリエチレングリコールモノアルキルエーテル、テトラエチレングリコールモノアルキルエーテル、ヘキサエチレングリコールモノアルキルエーテル、ヘプタエチレングリコールモノアルキルエーテル、ポリエチレングリコールモノアルキルエーテル、トリエチレングリコールモノアルキルエステル、テトラエチレングリコールモノアルキルエステル、ヘキサエチレングリコールモノアルキルエステル、ヘプタエチレングリコールモノアルキルエステル、ポリエチレングリコールモノアルキルエステル、トリエチレングリコールジアルキルエステル、トリプロピレングリコールモノアルキルエーテル、テトラプロピレングリコールモノアルキルエーテル、ヘキサプロピレングリコールモノアルキルエーテル、ヘプタプロピレングリコールモノアルキルエーテル、ポリプロピレングリコールモノアルキルエーテル等、更にテトラエチレングリコールモノアクリレート、ヘキサエチレングリコールモノアクリレート、ヘプタエチレングリコールモノアクリレート、ポリエチレングリコールモノアクリレート、トリエチレングリコールモノメタアクリレート、テトラエチレングリコールモノメタアクリレート、ヘキサエチレングリコールモノメタアクリレート、ヘプタエチレングリコールモノメタアクリレート、ポリエチレングリコールモノメタアクリレート、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシアルキレンラウリルエーテル、ポリオキシエチレンイソデシルエーテル、ポリオキシエチレンアルキルエーテル、ポリオキシアルキレンアルキルエーテル、ポリオキシエチレンヒマシ油、ポリオキシエチレン硬化ヒマシ油、ポリオキシエチレンスチレン化フェニルエーテル、ポリオキシエチレンオレイン酸エステル、ポリオキシエチレンジステアリン酸エステル、ポリオキシアルキレングリコール、ソルビタンセスキオレエート、ソルビタンモノオレエート、ソルビタンモノステアレート、ソルビタンモノラウレート、ポリオキシエチレンソルビタンモノラウレート、ポリオキシエチレンソルビタンモノステアレート、ポリオキシエチレンソルビタンモノオレエート、ポリオキシエチレンラノリンアルコールエーテル、ポリオキシエチレンラノリン脂肪酸エステル、ポリオキシエチレンアルキルアミンエーテル、ポリエチレングリコールアルキルエーテル、ポリエチレングリコールモノラウレート、ポリエチレングリコールモノステアレート、ポリエチレングリコールモノオレエート、ポリエチレングリコールソルビタンモノラウレート、ポリエチレングリコールソルビタンモノオレエートなどが挙げられる。これらのポリオキシアルキレン系化合物は、１種単独で、あるいは２種以上組み合わせて用いることができる。 Examples of the compound containing a skeleton represented by the general formula [III] include polyoxyalkylene compounds represented by the following general formula [VI].

In the general formula [VI], ^Rb is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and ^Ra is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. And an acyl group having 1 to 20 carbon atoms. k represents the average number of repeating units and is in the range of 1-100. Specific examples of such polyoxyalkylene compounds include triethylene glycol, tetraethylene glycol, hexaethylene glycol, heptaethylene glycol, polyethylene glycol, triethylene glycol monoalkyl ether, tetraethylene glycol monoalkyl ether, hexaethylene glycol mono Alkyl ether, heptaethylene glycol monoalkyl ether, polyethylene glycol monoalkyl ether, triethylene glycol monoalkyl ester, tetraethylene glycol monoalkyl ester, hexaethylene glycol monoalkyl ester, heptaethylene glycol monoalkyl ester, polyethylene glycol monoalkyl ester, Triethylene glycol dialkyl ester Ter, tripropylene glycol monoalkyl ether, tetrapropylene glycol monoalkyl ether, hexapropylene glycol monoalkyl ether, heptapropylene glycol monoalkyl ether, polypropylene glycol monoalkyl ether, etc., tetraethylene glycol monoacrylate, hexaethylene glycol monoacrylate, Heptaethylene glycol monoacrylate, polyethylene glycol monoacrylate, triethylene glycol monomethacrylate, tetraethylene glycol monomethacrylate, hexaethylene glycol monomethacrylate, heptaethylene glycol monomethacrylate, polyethylene glycol monomethacrylate, polyoxyethylene lauric Ether, polyoxyethylene oleyl ether, polyoxyalkylene lauryl ether, polyoxyethylene isodecyl ether, polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene styrene Phenyl ether, polyoxyethylene oleate, polyoxyethylene distearate, polyoxyalkylene glycol, sorbitan sesquioleate, sorbitan monooleate, sorbitan monostearate, sorbitan monolaurate, polyoxyethylene sorbitan monolaurate , Polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxy Ethylene lanolin alcohol ether, polyoxyethylene lanolin fatty acid ester, polyoxyethylene alkylamine ether, polyethylene glycol alkyl ether, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate, polyethylene glycol sorbitan monolaurate, polyethylene Examples include glycol sorbitan monooleate. These polyoxyalkylene compounds can be used singly or in combination of two or more.

In the examples to be described later, polyoxyalkylene glycol represented by the following general formula [VII] is preferably used from the viewpoints of availability, fouling suppression ability and the like. The skeleton-containing compound is not limited to this compound.

In the general formula [VII], m, n, and p represent the average number of repeating units, and m = 1 to 20, n = 2 to 50, and p = 1 to 20. R ^c represents an alkyl group having 1 to 10 carbon atoms, and a methyl group is preferably used because it is easily available. In the general formula [VII], the total of m and p (m + p) indicating the number of repeating units of the oxyethylene unit represented by (CH ₂ CH ₂ O) is 2 to 40, preferably 4 to 20, and more preferably. Is in the range of 4-15. The ratio (m / p) of the number of repeating units is 0.1 to 10, and preferably 0.5 to 5. On the other hand, a preferable range of n indicating the number of repeating units of the oxyalkylene unit represented by [CH ₂ CH (R ^c ) O] is 10 to 50, and a more preferable range is 20 to 50.

上記一般式[VIII]中、ｍは１〜３０、好ましくは６〜２０、より好ましくは７〜１７の範囲である。 Preferred examples of the compound containing a skeleton represented by the general formula [IV] include aliphatic diethanolamides represented by the following general formula [VIII].

In the above general formula [VIII], m is in the range of 1-30, preferably 6-20, more preferably 7-17.

  Preferred examples of such fatty acid diethanolamides include hexanoic acid diethanolamide, heptanoic acid diethanolamide, octanoic acid diethanolamide, nonanoic acid diethanolamide, decanoic acid diethanolamide, undecanoic acid diethanolamide, lauric acid diethanolamide, tridecylic acid. Examples include diethanolamide, myristic acid diethanolamide, pentadecyl acid diethanolamide, palmitic acid diethanolamide, heptadecanoic acid diethanolamide, stearic acid diethanolamide, and the like. Of these, lauric acid diethanolamide is particularly preferable. In addition to fatty acid diethanolamide, fatty acid dimethanolamide, fatty acid monomethanolamide, fatty acid monoethanolamide, fatty acid monopropanolamide and the like can be mentioned. These aliphatic amides can be used alone or in combination of two or more.

上記一般式［IX］中、Ｒ^dは水素原子又は１〜５０の炭素原子を有する線状又は分枝状アルキル基であり、Ｒ^eは（ＣＨ₂）_xＯＨ基（式中、ｘは１〜５０、好ましくは２〜２５の整数である）のようなヒドロキシアルキル基である。このような化合物の非限定例としては、Ｃ₁₈Ｈ₃₇Ｎ（ＣＨ₂ＣＨ₂ＯＨ）₂を有するケマミン（Kemamine）ＡＳ-９９０［テキサス、ヒューストンのウィトコ・ケミカル・コーポレーション（Witco Chemical Corporation）から入手可能）、Ｃ₁₂Ｈ₂₅Ｎ（ＣＨ₂ＣＨ₂ＯＨ）₂を有するケマミンＡＳ-６５０（ウィトコから入手可能）及びＩＣＩスペシャリテイーズから入手可能なアトマー１６３、和光純薬から入手可能なポリオキシエチレン（１０）ステアリルアミンエーテルを例示することができる。 Examples of the compound containing a skeleton represented by the general formula [V] include tertiary amine compounds represented by the following general formula [IX].

In the general formula [IX], R ^d is a hydrogen atom or a linear or branched alkyl group having 1 to 50 carbon atoms, and R ^e is a (CH ₂ ) _x OH group (wherein x is 1 To 50, preferably an integer of 2 to 25). Non-limiting examples of such compounds include Kemamine AS-990 with C ₁₈ H ₃₇ N (CH ₂ CH ₂ OH) ₂ (available from Witco Chemical Corporation, Houston, Texas). Possible), Chemamine AS-650 with C ₁₂ H ₂₅ N (CH ₂ CH ₂ OH) ₂ (available from Witco) and Atomer 163 available from ICI Specialties, polyoxyethylene available from Wako Pure Chemical ( 10) Stearylamine ether can be exemplified.

  (C) The oxyalkylene skeleton-containing compound is used in an amount of 0.1 to 10% by weight, more preferably 0.3 to 5% by weight, based on the solid content in the suspension obtained in Step P1. Further, the temperature is usually added at −78 ° C. to 100 ° C., more preferably 0 ° C. to 70 ° C., and the mixture is usually contact-mixed for 1 minute to 10 hours, preferably 10 minutes to 3 hours. The polyoxyalkylene compound may be diluted in a solvent. Preferred solvents include aromatic hydrocarbons such as toluene, xylene and benzene, saturated hydrocarbons such as hexane, heptane, decane and cyclohexane, ethers such as THF and diisopropyl ether, and halogenated hydrocarbons such as chloroform and chlorobenzene. More preferred are aromatic hydrocarbons such as toluene and xylene, and saturated hydrocarbons such as hexane, heptane and decane. The term “dilution” as used in the present invention refers to a mixture of a liquid inert to the oxyalkylene skeleton-containing compound (C) and the compound (C) or a dispersion of the compound (C). Including. That is, it is a solution or dispersion, and more specifically, a solution, suspension (suspension) or emulsion (emulsion). Among these, those in which the oxyalkylene skeleton-containing compound (C) and the solvent are mixed to form a solution are preferable.

  The (D) metallocene compound used in Step P2 is a transition metal compound containing a ligand having a cyclopentadienyl skeleton in the molecule. A transition metal compound containing a ligand having a cyclopentadienyl skeleton in the molecule is represented by a metallocene compound (D1) represented by the following general formula [X] and a general formula [XI] below from its chemical structure. It is classified into three types: a bridged metallocene compound (D2) and a constrained geometric compound (D3) represented by the following general formula [XII]. Among these, the metallocene compound (D1) and the bridged metallocene compound (D2) are preferable, and the metallocene compound (D2) is more preferable.

[In the above general formulas [X] and [XI], M represents a titanium atom, a zirconium atom, or a hafnium atom, and Q can be coordinated by a halogen atom, a hydrocarbon group, an anionic ligand, and a lone electron pair. Cyclopentadienyl selected from neutral ligands, j is an integer of 1 to 4, Cp ¹ and Cp ² may be the same or different from each other and can form a sandwich structure with M Or a substituted cyclopentadienyl group. Here, the substituted cyclopentadienyl group includes an indenyl group, a fluorenyl group, and a group in which these are substituted with one or more hydrocarbyl groups, and in the case of an indenyl group or a fluorenyl group, a cyclopentadienyl group. A part of the double bond may be hydrogenated to the benzene skeleton that condenses with benzene. In the general formula [XI], Y represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, or divalent germanium. -Containing group, divalent tin-containing group, -O-, -CO-, -S-, -SO-, -SO _2- , -Ge-, -Sn-, -NR ^a- , -P (R ^a ) -, - P (O) ( R a) -, - BR a - or -AlR ^a - it shows the. (However, R ^a may be the same or different from each other, and is a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom, a halogen atom, or a nitrogen atom. A nitrogen compound residue in which one or two hydrocarbon groups having 1 to 20 atoms are bonded. ]

[In the above general formula [XII], Ti represents a titanium atom in the oxidation state of +2, +3, and +4, and Cp ³ represents a cyclopentadienyl or substituted cyclopentadienyl group that is η-bonded to the titanium atom. X ¹ is an anionic ligand and X ² is a neutral conjugated diene compound. n + m is 1 or 2, Z is —O—, —S—, —NR ^b —, or —PR ^b —, and W is SiR ^b ₂ , CR ^b ₂ , SiR ^b ₂ —SiR ^b _2. , CR ^b ₂ -CR ^b ₂ , CR ^b = CR ^b , CR ^b ₂ -SiR ^b ₂ , GeR ^b ₂ , BR ^b ₂ , where R ^b is a hydrogen atom, hydrocarbyl group, silyl group, germanium group, Selected from cyano groups, halogen atoms or combinations thereof and combinations thereof having up to 20 non-hydrogen atoms. Examples of the substituted cyclopentadienyl group include one or more hydrocarbyl groups having 1 to 20 carbon atoms, halohydrocarbyl groups having 1 to 20 carbon atoms, halogen atoms, and hydrocarbyl having 1 to 20 carbon atoms. Examples include a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, a fluorenyl group, or an octafluorenyl group substituted with a substituted group 14 metalloid group, preferably substituted with an alkyl group having 1 to 6 carbon atoms. A cyclopentadienyl group; As X ¹ and X ² , for example, in the above general formula [XII], when n is 2, m is 0, and the oxidation number of titanium is +4, X ¹ is a carbon number such as a halogen atom, a methyl group, a benzyl group If 1 is selected from 1 to 20 alkyl groups or aralkyl groups, n is 1 and m is 0 and the oxidation number of titanium is +3, X ¹ is 2- (N, N-dimethyl) aminobenzyl, and further oxidation of titanium If the number is +4, X ¹ is 2-butene-1,4-diyl, and if n is 0, m is 1 and the oxidation number of titanium is +2, X ² is 1,4-diphenyl-1, A diene compound such as 3-butadiene or 1,3-pentadiene is selected. ]

The metallocene compound used in the examples described later is a compound represented by the following formula [XIII], a compound represented by the following formula [XIV], and a compound represented by the following formula [XV]. Is not limited by the compounds used in these examples.

  The metallocene compound (D) is mixed by contact after adding 0.1 to 10% by weight, more preferably 0.3 to 5% by weight, based on the solid content in the suspension obtained in the step P1. . The temperature at the time of addition and the temperature at the time of contact mixing are usually added at −78 ° C. to 100 ° C., more preferably 0 ° C. to 80 ° C., usually 1 minute to 10 hours, preferably 10 minutes to 3 hours. Let The metallocene compound may be used after diluted in a solvent. Solvents for such dilution include aromatic hydrocarbons such as toluene, xylene and benzene, saturated hydrocarbons such as hexane, heptane, decane and cyclohexane, ethers such as THF and diisopropyl ether, and halogenations such as chloroform and chlorobenzene. Although hydrocarbon etc. are mentioned, More preferable are aromatic hydrocarbons, such as toluene and xylene, and saturated hydrocarbons, such as hexane, heptane, decane, and cyclohexane.

  Further, (D) the metallocene compound may be previously brought into contact with the aforementioned component (B) group 13 element-containing compound of the periodic table. As component (B) for such preliminary contact, (b-1) an organoaluminum compound is preferably used, and triisobutylaluminum is more preferably used. The contact between the (D) metallocene compound and the (B) group 13 element-containing compound at the time of preliminary contact may be carried out in a solvent. In this case, a preferable solvent is for diluting the above-mentioned metallocene compound. Solvents of the same type as the solvent are mentioned, and aromatic hydrocarbons such as toluene and xylene, and saturated hydrocarbons such as hexane, heptane, decane and cyclohexane are particularly preferable.

  In another aspect of the present invention, the olefin polymerization solid catalyst (K) is prepolymerized with one or more olefins selected from ethylene and an α-olefin having 3 to 8 carbon atoms. It relates to the catalyst (K ′).

  Examples of the olefin used for the prepolymerization include ethylene and an α-olefin having 3 to 8 carbon atoms. Specific examples of the α-olefin having 3 to 8 carbon atoms include propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 3-methyl-1-pentene and 3-ethyl-1- Pentene, 1-hexene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, Examples thereof include 3-ethyl-1-hexene and 1-octene. Particularly preferred are ethylene, propylene, 1-hexene, 3-methyl-1-butene and 4-methyl-1-pentene. Two or more of these olefins may be copolymerized, or one or more olefins may be polymerized and then another olefin may be polymerized.

  The phase state of the prepolymerization is not particularly limited, but liquid phase polymerization is preferably employed. Preferred solvents for liquid phase polymerization include saturated hydrocarbons such as propane, butane, hexane, cyclohexane, heptane and decane, aromatic hydrocarbons such as toluene and xylene, and α-olefin itself as a solvent. A mixture of these may also be used.

  In the prepolymerization, an organoaluminum compound may coexist if necessary. Preferable organoaluminum compounds include the same compounds as (b-1), and particularly preferred are triisobutylaluminum, triethylaluminum, and diisobutylaluminum hydride. The concentration in the polymerization system is preferably 0.001 to 1000 mmol / L, more preferably 0.01 to 200 mmol / L.

  The prepolymerization amount is preferably 0.1 to 1000 g, more preferably 0.5 to 500 g, and particularly preferably 1 to 200 g per 1 g of the solid catalyst for olefin polymerization (K).

(2) Polymerization Method of Olefin The polymerization method of the present invention comprises the solid catalyst for olefin polymerization (K) or the prepolymerized solid catalyst (K ′) and, if necessary, the (B) periodic table. One or more polymerizable monomers selected from ethylene and olefins having 3 to 12 carbon atoms are polymerized in the presence of a Group 13 element-containing compound.

  The (B) group 13 element-containing compound of the periodic table is preferably an organoaluminum compound represented by the general formula [II], and triethylaluminum and triisobutylaluminum are particularly preferable. The concentration of the component (B) in the polymerization system is preferably 0.001 to 1000 mmol / L, more preferably 0.01 to 200 mmol / L.

  Examples of the olefin having 3 to 12 carbon atoms used in the present invention include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, and 3-methyl-1. -Pentene, 1-octene, 1-decene, 1-dodecene and the like. The polymerizable monomer used in the present invention is usually at least one selected from ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene.

 One of the preferred embodiments of the polymerization method of the present invention is a polymerizable monomer containing propylene as an essential component, preferably a main component, and optionally containing at least one selected from ethylene and an α-olefin having 4 to 10 carbon atoms. It is. These α-olefins may be copolymerized using two or more of them at the same time, or (co) polymers having different compositions may be produced after producing (co) polymers having a certain composition. As an example of continuously producing (co) polymers having two or more different compositions as described above, after producing a crystalline propylene (co) polymer, an amorphous propylene copolymer is subsequently produced. An example is a so-called block copolymer to be produced. In the present invention, “propylene is the main component” is defined as the propylene concentration in the total polymerizable monomer being 50 mol% or more.

 Another aspect of the preferred polymerization method of the present invention is a polymerizable monomer containing ethylene as an essential component, preferably a main component, and optionally containing one or more selected from α-olefins having 3 to 10 carbon atoms. It is. These α-olefins may be copolymerized using two or more at the same time. In the present invention, “ethylene is the main component” is defined as the ethylene concentration in the total polymerizable monomer being 50 mol% or more.

  In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization, or a gas phase polymerization method. Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, and methylcyclopentane. And alicyclic hydrocarbons such as benzene, toluene, xylene and the like; halogen atomized hydrocarbons such as ethylene dichloride, chlorobenzene and dichloromethane, and mixtures thereof. A so-called bulk polymerization method using liquefied olefin itself as a solvent can also be used. The present invention is preferably employed for bulk polymerization, suspension polymerization, and gas phase polymerization from the viewpoint that the decrease in polymerization activity is small and fouling is suppressed.

When the polymerization is carried out using the solid catalyst for olefin polymerization (K) or the prepolymerized solid catalyst (K ′), the component (K) or (K ′) The transition metal atom is usually used in such an amount that it is 10 ⁻¹⁰ to 10 ⁻² mol, preferably 10 ⁻⁹ to 10 ⁻³ mol. The polymerization temperature is usually in the range of −50 to + 200 ° C., preferably 0 to 170 ° C. The polymerization pressure is usually under conditions of normal pressure to 10 MPa gauge pressure, preferably normal pressure to 5 MPa gauge pressure, and the polymerization reaction can be performed in any of batch, semi-continuous and continuous methods. . The polymerization reaction can be performed in two or more stages with different reaction conditions.

  In order to adjust the molecular weight of the obtained polymer, it can be adjusted by allowing hydrogen molecules to be present in the polymerization system or changing the polymerization temperature. When hydrogen molecules are added, the amount is suitably about 0.001 to 100 NL per 1 kg of the obtained polymer.

(3) Olefin polymer particles One of the preferred embodiments of the olefin polymer particles of the present invention is that the repeating unit (U1) derived from propylene is 50 to 100 mol%, ethylene and an α-olefin having 4 to 10 carbon atoms. Propylene polymer particles containing one or more olefin repeating units (U2) selected from 0 to 50 mol%. The propylene polymer particles have a feature that the bulk density is 0.30 (g / ml) or more, preferably 0.35 (g / ml) or more, more preferably 0.38 (g / ml) or more. Have. Further, the melting point (Tm) of the propylene polymer particles is 130 ° C. or less, preferably 128 ° C. or less, more preferably 120 ° C. or less, or an amorphous propylene copolymer is used for all olefin polymers. It is characterized by containing 5% to 80% by weight, preferably 8% to 65% by weight.

In another preferred embodiment of the olefin polymer particles of the present invention, the repeating unit (U3) derived from ethylene is composed of 50 to 100 mol% of one or more olefins selected from α-olefins having 3 to 10 carbon atoms. It is an ethylene polymer particle which contains a repeating unit (U4) in the ratio of 0-50 mol%. The ethylene polymer particles of the present invention have a density of 870 to 1000 kg / m ³ , preferably 890 to 985 kg / m ³ , particularly preferably 895 to 980 kg / m ³ .

  The olefin polymer particles of the present invention are characterized by good fluidity. As an index of fluidity, Carr's index (Chem. Eng., 72, 163 (1965)) that comprehensively evaluates the angle of repose, the degree of compression, the spatula angle, and the uniformity is known.

The olefin polymer particles of the present invention are characterized by an angle of repose of 10 ° to 50 °, preferably 20 ° to 45 °, more preferably 23 ° to 40 °. The degree of compression is usually 1% to 25%, preferably 3 to 20%, more preferably 4% to 15%.
The spatula angle is usually 10 ° to 60 °, preferably 20 ° to 55 °, more preferably 25 ° to 45 °. The uniformity is usually 1 to 12, preferably 1 to 8, more preferably 1 to 5.

  The olefin polymer particles of the present invention are characterized by a Carr index of 70 to 100 points, preferably 80 to 100 points.

  The olefin polymer particles of the present invention are excellent in flexibility, transparency and heat sealability, and are suitably used for films, sheets, stretched tapes, fibers and the like.

[Example]
EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention does not receive a restriction | limiting at all in these Examples. The catalyst production examples and polymerization examples shown below were carried out in a dry nitrogen atmosphere unless otherwise specified. In the examples, various physical properties were measured as follows.

[Melting point (Tm), heat of fusion (ΔH)]
Using a Diamond DSC manufactured by PerkinElmer, under a nitrogen atmosphere (20 ml / min), a sample of about 5 mg was heated to 230 ° C. and held for 10 minutes, and then cooled to 30 ° C. at 10 ° C./min. After maintaining at 30 ° C. for 1 minute, the melting point was calculated from the peak of the crystal melting peak when the temperature was raised to 230 ° C. at 10 ° C./min, and the heat of fusion was calculated from the integrated value of the peaks.

[Molecular weight distribution (Mw / Mn)]
The molecular weight distribution (Mw / Mn) was measured as follows using a gel permeation chromatograph Alliance GPC-2000 manufactured by Waters. The separation columns are two TSKgel GNH6-HT and two TSKgel GNH6-HTL, the column size is 7.5 mm in diameter and 300 mm in length, the column temperature is 140 ° C., and the mobile phase is o -Using dichlorobenzene (Wako Pure Chemical Industries) and 0.025 wt% BHT (Takeda Pharmaceutical) as an antioxidant, moving at 1.0 ml / min, sample concentration 15 mg / 10 mL, sample injection volume 500 micron A differential refractometer was used as a detector. The standard polystyrene used was manufactured by Tosoh Corporation for molecular weights of Mw <1000 and Mw> 4 × 10 ⁶ , and used by Pressure Chemical Co. for 1000 ≦ Mw ≦ 4 × 10 ⁶ .

[Intrinsic viscosity (η)]
It is a value measured at 135 ° C. using a decalin solvent. That is, about 20 mg of polymer powder or resin mass is dissolved in 15 ml of decalin, and the specific viscosity η _sp is measured in an oil bath at 135 ° C. After adding 5 ml of decalin solvent to this decalin solution for dilution, the specific viscosity η _sp is measured in the same manner. This dilution operation is further repeated twice, and the value of η _sp / C when the concentration (C) is extrapolated to 0 is obtained as the intrinsic viscosity (see the following formula).
(Η) = lim (η _sp / C) (C → 0)

[MFR]
Using a TP-406 type MFR meter manufactured by Tester Sangyo Co., Ltd., BHT was added as a stabilizer, and a preheating time of 6 minutes was measured at 230 ° C. under a load of 2.16 kgf.

[Rough grain amount]
Propylene-based polymer: The polymer particles were vibrated on a sieve having an opening of 1 mm, and the polymer weight% remaining on the sieve was measured.
Ethylene polymer: Polymer particles were vibrated on a sieve having an opening of 1.7 mm, and the polymer weight% remaining on the sieve was measured.

[The bulk density]
Measurements were performed according to ASTM D1895-96 A method.

[Ethylene content]
Using a Fourier transform infrared spectrophotometer FT / IR-610 manufactured by JASCO Corporation, the area near the rolling vibration 733 cm ⁻¹ based on the methylene group and the absorbance near the harmonic overtone 4325 cm ⁻¹ due to the C—H stretching vibration are obtained. The ratio was calculated from a calibration curve (prepared using a standard sample standardized by ¹³ C-NMR).

[Repose angle, degree of compression, spatula angle]
Measurement was performed using a multifunctional powder property measuring instrument (multi-tester) MT-1001 manufactured by Seishin Enterprise Co., Ltd.

[Uniformity]
Using a particle size analyzer Microtrac 9320-X100 manufactured by Leeds & Northrup, methanol was used as a dispersion medium, and the particle size distribution was measured by dispersing with an ultrasonic homogenizer for 5 minutes (output: 25 W). The uniformity was calculated from the obtained result and the following formula.
Uniformity = D _p60 / D _p10
D _p60 : Particle diameter corresponding to 60% cumulative weight from the small diameter side in the particle size distribution D _p10 : Particle diameter corresponding to 10% cumulative weight from the small diameter side in the particle size distribution

[density]
A sheet of 0.5 mm thickness was formed at a pressure of 100 kg / cm ² using a hydraulic heat press machine manufactured by Shindo Metal Industry Co., Ltd. set at 190 ° C. (spacer shape: 45 × on a 240 × 240 × 0.5 mm thick plate) 45 × 0.5 mm, 9 pieces), using another hydraulic hot press machine manufactured by Shinfuji Metal Industry Co., Ltd. set to 20 ° C., and cooled by compressing at a pressure of 100 kg / cm ² to prepare a measurement sample. . As the hot plate, a 5 mm thick SUS plate was used.
The press sheet was heat-treated at 120 ° C. for 1 hour, linearly cooled to room temperature over 1 hour, and then measured with a density gradient tube.

[Loss of burning]
The measurement was performed using a differential thermal balance TG8120 manufactured by Rigaku Corporation. Using alumina as a reference substance, about 10 mg of a sample was collected in the air, heated to 600 ° C. at a rate of 5 ° C./min, and held at 600 ° C. for 30 minutes. Based on the weight at 200 ° C. at this time, the weight loss rate (% by weight) at 200 ° C. to 600 ° C. was defined as a loss on ignition.

[Elemental analysis]
Measurement was performed using ICP (Inductively Coupled Plasma) emission spectroscopic analyzer manufactured by Shimadzu Corporation: ICPS-8100 type. For quantification and qualitative analysis of aluminum and zirconium, the sample was subjected to wet decomposition with sulfuric acid and nitric acid, and then a constant volume (including filtration and dilution as necessary) was used as a test solution. For quantitative and qualitative analysis of silicon, a sample was melted with sodium carbonate, dissolved by adding hydrochloric acid, and a constant volume and diluted sample was used as a test solution.

-Production of solid catalyst (K) for olefin polymerization-
[Process P1]
A 100 ml four-necked flask fully purged with nitrogen was equipped with a stir bar, and 5.01 g of silica gel (trade name: H-122, manufactured by Asahi S-Tech Co., Ltd.) dried at 200 ° C. in a nitrogen atmosphere, 44 ml of dehydrated toluene Was added and the temperature was raised to 50 ° C. by overheating in an oil bath. 2.5 ml of a toluene solution (1M) of triisobutylaluminum was added, and 19.0 ml of a toluene solution of methylaluminoxane (produced by Tosoh Finechem Co., Ltd., aluminum concentration 9.1% by weight) was further added. The mixture was reacted at 50 ° C. for 30 minutes, and further reacted at 95 ° C. for 4 hours. After standing at 60 ° C., 36 mL of the supernatant was removed by decantation to obtain a toluene slurry of silica-supported methylaluminoxane.

[Process P2]
The toluene slurry of silica-supported methylaluminoxane obtained in Step P1 was kept at 35 ° C., and 10 ml of hexane was added thereto, followed by polyalkyleneoxy glycol (trade name: Adeka Pluronic L-71, manufactured by Asahi Denka Kogyo Co., Ltd. 20 ml of a 1.5% by weight hexane solution. After reacting for 45 minutes, diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (2,7-di-tert-butyl-fluorenyl), a transition metal compound, previously mixed A mixture of 149 mg of zirconium dichloride (produced by the method described in WO2004 / 087775), 1.86 ml of a toluene solution (1M) of triisobutylaluminum and 4 ml of hexane was added. After reacting for 1 hour, the resulting slurry was filtered through a membrane filter. The obtained powder was dried under reduced pressure for 2 hours to obtain 9.45 g of a powdery solid catalyst (K). This was mixed with dehydrated liquid paraffin to make a 20.0 wt% slurry. As a result of analysis, zirconium in the powder was 0.17% by weight and aluminum was 17.6% by weight. The loss on ignition was 13.5% by weight. Elemental analysis of the residue after ignition confirmed peaks based on silicon atoms and aluminum atoms.

  Manufactured in the same manner as in Example 1 except that silica gel (product name: H-122, manufactured by Asahi S-Tech Co., Ltd.) was used to remove fine particles having a diameter of 4 μm or less by classification, and 16.8 ml of a toluene solution of methylaluminoxane was used. Went. As a result of analysis, zirconium in the powder was 0.18% by weight, aluminum was 16.7% by weight, and silicon was 23.2% by weight. The loss on ignition was 14.1% by weight. Further, when the residue was subjected to elemental analysis after heating, peaks based on silicon atoms and aluminum atoms were confirmed.

-Production of solid catalyst for olefin polymerization (K ')-
To a 200 mL flask, 10.02 g of the liquid paraffin slurry produced in Example 2, 6.51 g of the filtrate obtained by filtering with a membrane filter and 30 ml of hexane were added, and the mixture was heated to 34 ° C. To this, 2.0 ml of a 1 mol / L triisobutylaluminum hexane solution and 2 ml of a 10 g / L hexane solution of polyalkyleneoxy glycol (trade name: Adeka Pluronic L-71, manufactured by Asahi Denka Kogyo Co., Ltd.) were added. Ethylene was blown into the gas phase at a rate of 1.5 NL / h, and polymerization was carried out at 35 ° C. for 4 hours. The residual ethylene was purged with nitrogen, and the resulting slurry was filtered through a membrane filter. Drying was performed under reduced pressure for 3 hours to obtain 7.56 g of a solid catalyst (K ′).

-Homopolymerization of propylene (1)-
A magnetic stirrer was placed in a 50 ml branch flask thoroughly purged with nitrogen, and 803 mg of the slurry of the solid catalyst (K) prepared in Example 1 above and a hexane solution of triisobutylaluminum (Al = 1.0 M). 1.0 mmol and 5.0 ml of dehydrated hexane were added, and the mixture was introduced into a 2,000-ml SUS autoclave thoroughly purged with nitrogen. Thereafter, 500 g of liquid propylene was charged and polymerization was performed at 70 ° C. for 40 minutes, and then the polymerization was stopped by cooling the autoclave and purging propylene. The polymer was dried under reduced pressure at 80 ° C. for 10 hours.
The obtained polymer was 125.8 g of isotactic polypropylene, and the polymerization activity was 62.3 kg-PP / mmol-Zr · hr. As a result of polymer analysis, (η) = 0.27 dl / g, MFR = 0.30 g / 10 min, bulk density was 0.49 g / cm ³ , and the amount of coarse particles was 2.2% by weight. In addition, adhesion of the polymer was not seen in the autoclave.

-Homopolymerization of propylene (2)-
Polymerization was carried out under the same conditions as in Example 4 except that 352 mg of the slurry of the solid catalyst (K) prepared in Example 1 was used, 500 g of liquid propylene was charged, and 0.08 NL of hydrogen was added. went.
The obtained polymer was 160.2 g of isotactic polypropylene, and the polymerization activity was 181 kg-PP / mmol-Zr · hr. As a result of polymer analysis, (η) = 2.30 dl / g, MFR = 2.38 g / 10 min, bulk density was 0.50 g / cm ³ , and the amount of coarse particles was 0.11% by weight. Uniformity was 2, repose angle was 28 °, compression degree was 10%, spatula angle was 30 °, and Carr's index was 93.5 points. In addition, adhesion of the polymer was not seen in the autoclave.

-Homopolymerization of propylene (3)-
A magnetic stirrer was placed in a 50 ml branch flask thoroughly purged with nitrogen, and 802 mg of the slurry of the solid catalyst (K) prepared in Example 2 above and a hexane solution of triisobutylaluminum (Al = 1.0 M). 1.0 mmol and 5.0 ml of dehydrated hexane were added, and the mixture was introduced into a 2,000-ml SUS autoclave thoroughly purged with nitrogen. Thereafter, 500 g of liquid propylene was charged and polymerization was performed at 70 ° C. for 40 minutes, and then the polymerization was stopped by cooling the autoclave and purging propylene. The polymer was dried under reduced pressure at 80 ° C. for 10 hours.
The obtained polymer was 143.1 g of isotactic polypropylene, and the polymerization activity was 66.1 kg-PP / mmol-Zr · hr. As a result of polymer analysis, (η) = 3.18 dl / g, MFR = 0.32 g / 10 min, Mw = 558,000, Mw / Mn = 3.1, Tm = 144.0 ° C., ΔH = 86.0 J / g, bulk density is 0.50 g / cm ³ , and the amount of coarse particles was 0.0% by weight. In addition, adhesion of the polymer was not seen in the autoclave.

-Homopolymerization of propylene (4)-
Polymerization was carried out under the same conditions as in Example 6 except that 356 mg of the slurry of the solid catalyst (K) prepared in Example 2 was used, 500 g of liquid propylene was charged, and 0.08 NL of hydrogen was added. went.
The obtained polymer was 159.6 g of isotactic polypropylene, and the polymerization activity was 166.2 kg-PP / mmol-Zr · hr. As a result of polymer analysis, (η) = 2.32 dl / g, MFR = 1.85 g / 10 min, Mw = 330,000, Mw / Mn = 2.7, Tm = 146.7 ° C., ΔH = 88.6 J / g, bulk density is 0.51 g / cm ³ , and the amount of coarse particles was 0.0% by weight. In addition, adhesion of the polymer was not seen in the autoclave.

-Homopolymerization of propylene (5)-
A magnetic stirring bar was placed in a 50-ml branch flask thoroughly purged with nitrogen, and 641 mg of the solid catalyst (K ′) prepared in Example 3 above and a hexane solution of triisobutylaluminum (Al = 1.0 M) 1.0 mmol and 5.0 ml of dehydrated hexane were added, and the mixture was introduced into a 2,000-ml SUS autoclave sufficiently purged with nitrogen. Thereafter, 500 g of liquid propylene was charged and polymerization was performed at 70 ° C. for 40 minutes, and then the polymerization was stopped by cooling the autoclave and purging propylene. The polymer was dried under reduced pressure at 80 ° C. for 10 hours.
The obtained polymer was 122.9 g of isotactic polypropylene, and the polymerization activity was 55.1 kg-PP / mmol-Zr · hr. As a result of polymer analysis, (η) = 3.58 dl / g, MFR = 0.25 g / 10 min, bulk density was 0.49 g / cm ³ , and the amount of coarse particles was 0.0% by weight. In addition, adhesion of the polymer was not seen in the autoclave.

-Homopolymerization of propylene (6)-
Polymerization was carried out under the same conditions as in Example 8 except that 283 mg of the solid catalyst (K ′) prepared in Example 3 was used, 500 g of liquid propylene was charged, and 0.08 NL of hydrogen was added. .
The obtained polymer was 170.5 g of isotactic polypropylene, and the polymerization activity was 172.9 kg-PP / mmol-Zr · hr. As a result of polymer analysis, (η) = 2.24 dl / g, MFR = 2.67 g / 10 min, bulk density was 0.50 g / cm ³ , and the amount of coarse particles was 0.0% by weight. In addition, adhesion of the polymer was not seen in the autoclave.

-Random polymerization of propylene (1)-
A magnetic stirring bar was placed in a 50-ml branch flask thoroughly purged with nitrogen, and 160 mg of the slurry of the solid catalyst (K) prepared in Example 2 above and a hexane solution of triisobutylaluminum (Al = 1.0M). 1.0 mmol and 5.0 ml of dehydrated hexane were added, and the mixture was introduced into a 2,000-ml SUS autoclave thoroughly purged with nitrogen. Thereafter, 500 g of liquid propylene was charged, and 3.0 NL of ethylene was charged, followed by 0.3 NL of hydrogen. After polymerization at 60 ° C. for 40 minutes, the autoclave was cooled and purged with propylene to stop the polymerization. The polymer was dried under reduced pressure at 80 ° C. for 10 hours.
The obtained polymer was 243.5 g of an ethylene-propylene copolymer, and the polymerization activity was 562.8 kg-PP / mmol-Zr · hr. As a result of polymer analysis, (η) = 1.44 dl / g, MFR = 23.6 g / 10 min, ethylene content 2.53 mol%, Tm = 131.3 ° C., ΔH = 85.7 J / g, bulk density 0.42 g / cm ³ , The amount of coarse particles was 0.12% by weight. Uniformity was 2, repose angle was 32 °, compression was 8%, spatula angle was 37 °, and Carr's index was 88 points.

-Random polymerization of propylene (2)-
Polymerization was carried out under the same conditions as in Example 10 except that 157 mg of the slurry of the solid catalyst (K) prepared in Example 2 was used, 500 g of liquid propylene was charged, and 0.6 NL of hydrogen was added. went.
The obtained polymer was 271.0 g of an ethylene-propylene copolymer, and the polymerization activity was 638.3 kg-PP / mmol-Zr · hr. As a result of polymer analysis, (η) = 0.96 dl / g, MFR = 175 g / 10 min, ethylene content 2.68 mol%, Tm = 131.5 ° C., ΔH = 76.2 J / g, bulk density 0.44 g / cm ³ , The amount of coarse particles was 0.53% by weight.

-Random polymerization of propylene (3)-
Polymerization was performed under the same conditions as in Example 10 except that 89 mg of the solid catalyst (K) slurry prepared in Example 2 was used and polymerized for 30 minutes.
The obtained polymer was 143.2 g of an ethylene-propylene copolymer, and the polymerization activity was 795.3 kg-PP / mmol-Zr · hr. As a result of polymer analysis, (η) = 1.97 dl / g, MFR = 13.7 g / 10 min, ethylene content 3.70 mol%, Tm = 123.2 ° C., ΔH = 66.4 J / g, bulk density 0.38 g / cm ³ , The amount of coarse particles was 0.13% by weight. Uniformity was 2, repose angle was 36 °, compression degree was 7%, spatula angle was 39 °, and Carr's index was 85 points.

-Extraction test of solid catalyst (K) for olefin polymerization (1)-
In a dry nitrogen atmosphere, 150 mg of the powdered solid catalyst (K) produced in Example 1 was weighed. 7.5 g of dry hexane was added thereto, and the mixture was stirred for 1 hour in an atmosphere at 22 ° C. The obtained slurry was filtered using a Teflon (registered trademark) membrane filter having a pore diameter of 3 μm. The obtained filtrate was concentrated under reduced pressure, and dried under reduced pressure at 3 hPa for 3 hours in an atmosphere at 22 ° C. The obtained non-volatile component was 0.3 mg.

-Extraction test of solid catalyst (K) for olefin polymerization (2)-
In a dry nitrogen atmosphere, 150 mg of the powdered solid catalyst (K) produced in Example 1 was weighed. This was left still in a desiccator equipped with a saturated aqueous potassium acetate solution and contacted with water vapor for 7 days. After removing from the desiccator, 1 g of deuterated acetonitrile was added in the atmosphere and stirred for 30 minutes. Filtration was performed through a glass tube filled with glass wool, and the obtained filtrate was subjected to ¹ H-NMR measurement. The NMR chart is shown in FIG. A peak derived from an oxymethylene group was confirmed at 3.2 to 3.3 ppm. The standard of chemical shift was the peak of residual proton of acetonitrile (1.93 ppm).

-Production of solid catalyst (K) for olefin polymerization-
Using silica gel from which fine particles having a diameter of 4 μm or less were removed, a toluene slurry of silica-supported methylaluminoxane was produced in the same manner as in Example 1 and Step P1, and prepared at 180 g / L. A 100-ml four-necked flask thoroughly purged with nitrogen was equipped with a stirring rod, and 11.1 ml of this slurry and 30 ml of toluene were charged. 1.0 ml of a 10 g / L hexane suspension of polyoxyethylene (10) stearylamine ether (Wako Pure Chemical Industries, Ltd.) was added. Diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (2,7-di-tert-butyl), a pre-mixed transition metal compound, after reacting at 35 ° C. for 45 minutes -Fluorenyl) zirconium dichloride (manufactured by the method described in WO2004 / 087775) A mixture of 33.5 mg, 0.9 ml of a toluene solution of triisobutylaluminum (0.5 M) and 4 ml of toluene was added. After reacting for 1 hour, the resulting slurry was filtered through a membrane filter, washed twice with 15 ml of hexane, and then filtered. Further, the resultant was washed with 15 ml of hexane, filtered, and the obtained filtrate was concentrated under reduced pressure. As a result, the residue was less than 0.1 mg. The obtained powder was dried under reduced pressure for 2 hours to obtain 2.09 g of a powdery solid catalyst. This was mixed with dehydrated liquid paraffin to make a 20.0 wt% slurry. As a result of analysis, zirconium in the powder was 0.17% by weight and aluminum was 16.9% by weight. The loss on ignition was 11.2% by weight. Further, when the residue was subjected to elemental analysis after heating, peaks based on silicon atoms and aluminum atoms were confirmed.

-Homopolymerization of propylene (7)-
A magnetic stirring bar was placed in a 50 ml branch flask thoroughly purged with nitrogen, to which 599 mg of the solid catalyst slurry prepared in Example 15 above and 0.75 mmol of a hexane solution of triisobutylaluminum (Al = 0.5M) and 5.0 ml of dehydrated hexane was added, and the mixture was introduced into an autoclave made of SUS with an internal volume of 3,400 ml that was sufficiently purged with nitrogen. Thereafter, 750 g of liquid propylene was charged, 0.08 NL of hydrogen was added, polymerization was performed at 70 ° C. for 40 minutes, and then the autoclave was cooled and propylene was purged to stop the polymerization. The polymer was dried under reduced pressure at 80 ° C. for 10 hours. The obtained polymer was 183.3 g of isotactic polypropylene, and the polymerization activity was 120.4 kg-PP / mmol-Zr · hr. As a result of polymer analysis, (η) = 2.60 dl / g, MFR = 1.17 g / 10 min, bulk density was 0.50 g / cm ³ , and the amount of coarse particles was 0.1% by weight. Uniformity was 2, repose angle was 28 °, compression degree was 11%, spatula angle was 26 °, and Carr's index was 93 points.

-Homopolymerization of propylene (8)-
Polymerization was carried out under the same conditions as in Example 15 except that 539 mg of the solid catalyst slurry prepared in Example 15 was used, 750 g of liquid propylene was charged, and then 0.16 NL of hydrogen was added. The obtained polymer was 285.0 g of isotactic polypropylene, and the polymerization activity was 208 kg-PP / mmol-Zr · hr. As a result of polymer analysis, (η) = 1.86 dl / g, MFR = 6.9 g / 10 min, bulk density was 0.50 g / cm ³ , and the amount of coarse particles was 0.2% by weight. Uniformity was 2, repose angle was 28 °, compression degree was 11%, spatula angle was 27 °, and Carr's index was 93 points.

-Homopolymerization of propylene (9)-
A magnetic stirring bar was placed in a 50 ml branch flask thoroughly purged with nitrogen, and 502 mg of the solid catalyst slurry prepared in Example 2 above and 0.75 mmol of hexane solution of triisobutylaluminum (Al = 0.5M) and 5.0 ml of dehydrated hexane was added, and the mixture was introduced into an autoclave made of SUS with an internal volume of 3,400 ml that was sufficiently purged with nitrogen. Thereafter, 750 g of liquid propylene was charged, 0.08 NL of hydrogen was added, polymerization was performed at 70 ° C. for 40 minutes, and then the autoclave was cooled and propylene was purged to stop the polymerization. The polymer was dried under reduced pressure at 80 ° C. for 10 hours. The obtained polymer was 185.9 g of isotactic polypropylene, and the polymerization activity was 137.1 kg-PP / mmol-Zr · hr. As a result of polymer analysis, (η) = 2.54 dl / g, MFR = 1.15 g / 10 min, bulk density was 0.49 g / cm ³ , and the amount of coarse particles was 0.1% by weight.

-Homopolymerization of propylene (10)-
Polymerization was carried out under the same conditions as in Example 18 except that hydrogen 0.16NL was added. The obtained polymer was 286.2 g of isotactic polypropylene, and the polymerization activity was 211 kg-PP / mmol-Zr · hr. As a result of polymer analysis, (η) = 1.98 dl / g, MFR = 4.9 g / 10 min, bulk density was 0.50 g / cm ³ , and the amount of coarse particles was 0.0% by weight.

-Extraction test of solid catalyst (K) for olefin polymerization (3)-
Under a dry nitrogen atmosphere, 500 mg of the powdered solid catalyst (K) produced in Example 15 was weighed. 7.5 g of dry hexane was added thereto, and the mixture was stirred for 1 hour in an atmosphere at 22 ° C. The obtained slurry was filtered using a Teflon (registered trademark) membrane filter having a pore diameter of 3 μm. The obtained filtrate was concentrated under reduced pressure, and dried under reduced pressure at 3 hPa for 3 hours in an atmosphere at 22 ° C. The obtained non-volatile component was less than 0.1 mg.

-Extraction test of solid catalyst (K) for olefin polymerization (4)-
Under a dry nitrogen atmosphere, 500 mg of the powdered solid catalyst (K) produced in Example 15 was weighed. This was left still in a desiccator equipped with a saturated aqueous potassium acetate solution and contacted with water vapor for 7 days. After removing from the desiccator, 1.5 g of deuterated acetonitrile was added in the atmosphere and stirred for 30 minutes. Filtration was performed through a glass tube filled with glass wool, and the obtained filtrate was subjected to ¹ H-NMR measurement. A peak derived from an oxymethylene group was confirmed at 3.2 to 3.3 ppm. The standard of chemical shift was the peak of tetramethylsilane.

-Production of solid catalyst (K) for olefin polymerization-
A toluene slurry of silica-supported methylaluminoxane was produced by the method described in JP-A-2000-327707 and adjusted to a concentration of 200 g / L. The toluene slurry of 24 ml of silica-supported methylaluminoxane and 16 ml of toluene were charged into a 100 ml three-necked flask. To this, 3.6 ml of a 20 g / L hexane solution of polyalkyleneoxyglycol (trade name: Adeka Pluronic L-71, manufactured by Asahi Denka Kogyo Co., Ltd.) was added. After reacting for 30 minutes, 45 mg of toluene slurry of ethylenebis (indenyl) zirconium dichloride was added. After reacting for 1 hour, the resulting slurry was filtered through a membrane filter. Washed twice with 10 ml hexane. (The whole filtrate was concentrated under reduced pressure, but the residue was 0.1 mg or less.) Further, the filtrate was concentrated under reduced pressure by washing with 10 ml of hexane, but the residue was 0.1 mg or less. The obtained powder was dried under reduced pressure for 2 hours to obtain 4.82 g of powder. This was mixed with dehydrated liquid paraffin to make a 20.0 wt% slurry. As a result of analysis, the zirconium content in the supported catalyst was 0.18% by weight, and aluminum was 11.8% by weight. The loss on ignition was 7.79% by weight. Further, as a result of elemental analysis of the residue after heating, peaks based on silicon atoms and aluminum atoms were confirmed.

-Slurry polymerization of ethylene-
500 ml of heptane was charged into a 1,000 ml SUS autoclave which had been sufficiently purged with nitrogen. Ethylene gas was circulated to saturate the autoclave with ethylene. To this, 0.25 mmol of hexane solution of triisobutylaluminum (Al = 0.5M) was added. On the other hand, 0.133 g of the slurry of the supported catalyst prepared in Example 22 was weighed into a 50 ml flask with a three-way cock, and 4 ml of heptane in the autoclave was transferred thereto and stirred. The obtained catalyst slurry was charged into an autoclave. 4 ml of heptane was transferred from the autoclave to the flask, and the catalyst was added to the autoclave by charging the autoclave again. Thereafter, 5 ml of 1-hexene was charged, ethylene was continuously supplied at 0.8 ° C. at 80 ° C., and polymerization was carried out for 65 minutes. The polymerization was stopped by cooling the autoclave and purging the residual gas. No polymer adhesion was observed on the inner wall of the polymerization vessel. The obtained polymer slurry was filtered with a Kiriyama funnel (φ95 mm, filter paper No. 5B). There was no clogging of filter paper. The polymer was dried under reduced pressure at 80 ° C. for 10 hours. The obtained polymer was 44.7 g, and the polymerization activity was 80.4 kg-PE / mmol-Zr · hr. As a result of polymer analysis, the bulk density was 0.38 g / cm ³ and the density was 930 kg / m ³ .

-Ethylene gas phase polymerization-
500 g of sodium chloride was charged into a SUS autoclave with an internal volume of 1,000 ml that had been sufficiently purged with nitrogen. After sufficiently drying under heating, the mixture was cooled, ethylene gas was circulated, and the inside of the autoclave was saturated with ethylene. To this was added 0.25 mmol of triisobutylaluminum in hexane (Al = 0.5M). Meanwhile, 0.312 g of the slurry of the supported catalyst prepared in Example 22 and 0.13 mmol of a hexane solution of triisobutylaluminum (Al = 0.5M) were added to a 50 ml three-way cocked flask. The obtained catalyst slurry was charged into an autoclave. Thereafter, the inside of the autoclave was replaced with ethylene gas containing 4.0% by weight of 1-butene, and an ethylene / butene mixed gas was supplied at 80 ° C. so that the pressure became 0.8 MPa, and polymerization was performed for 60 minutes. The polymerization was stopped by cooling the autoclave and purging the residual gas. After 2 L of water was added to the obtained powder and stirred, the polymer slurry was exposed and filtered. After washing the polymer, it was dried under reduced pressure at 80 ° C. for 10 hours. The obtained polymer was 30.9 g, and the polymerization activity was 23.5 kg-PE / mmol-Zr · hr. As a result of polymer analysis, the amount of coarse particles was 1.5% by weight, the bulk density was 0.31 g / cm ³ , the density was 922 kg / m ³ , and (η) = 1.62 dl / g.

-Extraction test of solid catalyst (K) for olefin polymerization (5)-
Under a dry nitrogen atmosphere, 500 mg of the powdered solid catalyst (K) produced in Example 22 was weighed. 7.5 g of dry hexane was added thereto, and the mixture was stirred for 1 hour in an atmosphere at 23 ° C. The obtained slurry was filtered using a Teflon (registered trademark) membrane filter having a pore diameter of 3 μm. The obtained filtrate was concentrated under reduced pressure, and dried under reduced pressure at 3 hPa for 3 hours in an atmosphere at 22 ° C. The obtained non-volatile component was less than 0.1 mg.

-Extraction test of solid catalyst (K) for olefin polymerization (6)-
Under a dry nitrogen atmosphere, 500 mg of the powdered solid catalyst (K) produced in Example 22 was weighed. This was left still in a desiccator equipped with a saturated aqueous potassium acetate solution and contacted with water vapor for 7 days. After removing from the desiccator, 1.5 g of deuterated acetonitrile was added in the atmosphere and stirred for 30 minutes. Filtration was performed through a glass tube filled with glass wool, and the obtained filtrate was subjected to ¹ H-NMR measurement. A peak derived from an oxymethylene group was confirmed at 3.2 to 3.7 ppm. The standard of chemical shift was the peak of tetramethylsilane.

-Production of solid catalyst (K) for olefin polymerization-
Using silica gel from which fine particles having a diameter of 4 μm or less were removed, a toluene slurry of silica-supported methylaluminoxane was produced in the same manner as in Example 1 and Step P1, and prepared at 180 g / L. A 200 ml four-necked flask thoroughly purged with nitrogen was equipped with a stir bar, and 11.1 ml of this slurry and 30 ml of toluene were charged. Subsequently, 2 ml of a 20 g / L hexane solution of polyalkyleneoxy glycol (trade name: Adeka Pluronic L-71, manufactured by Asahi Denka Kogyo Co., Ltd.) was added and reacted at 35 ° C. for 45 minutes. Thereto was added a mixture of 5 ml of a toluene suspension of 30.2 mg of rac-dimethylsilylenebis (2-methyl-4-phenylindene) zirconium dichloride, which is a transition metal compound. After reacting for 1 hour, the obtained slurry was filtered with a membrane filter, washed twice with 15 ml of hexane and filtered (the whole filtrate was concentrated under reduced pressure, but the residue was 0.1 mg or less). Further, the resultant was washed with 15 ml of hexane, filtered, and the obtained filtrate was concentrated under reduced pressure. As a result, the residue was less than 0.1 mg. The obtained powder was dried under reduced pressure for 2 hours to obtain 2.08 g of a powdery solid catalyst. As a result of analysis, zirconium in the powder was 0.18% by weight and aluminum was 17.0% by weight. This was mixed with dehydrated liquid paraffin to make a 10.0 wt% slurry.

-Homopolymerization of propylene (11)-
A magnetic stirring bar was placed in a 50 ml branch flask thoroughly purged with nitrogen, and 598 mg of the slurry of the solid catalyst (K) prepared in Example 27 and a hexane solution of triisobutylaluminum (Al = 1.0 M). 0.75 mmol and 5.0 ml of dehydrated hexane were added, and the mixture was introduced into an autoclave made of SUS having an internal volume of 3,400 ml which was sufficiently purged with nitrogen. Thereafter, 750 g of liquid propylene was charged and polymerization was performed at 70 ° C. for 40 minutes, and then the polymerization was stopped by cooling the autoclave and purging with propylene. The polymer was dried under reduced pressure at 80 ° C. for 10 hours.
The obtained polymer was 138.8 g of isotactic polypropylene, and the polymerization activity was 179 kg-PP / mmol-Zr · hr. As a result of polymer analysis, MFR <0.01 g / 10 min, (η) = 6.71 dl / g, bulk density was 0.47 g / cm ³ , and the amount of coarse particles was 1.2% by weight. In addition, adhesion of the polymer was not seen in the autoclave.

-Extraction test of solid catalyst (K) for olefin polymerization (7)-
Under a dry nitrogen atmosphere, 200 mg of the powdered solid catalyst (K) produced in Example 27 was weighed. This was left still in a desiccator equipped with a saturated aqueous potassium acetate solution and contacted with water vapor for 7 days. After removing from the desiccator, 1.5 g of deuterated acetonitrile was added in the atmosphere and stirred for 30 minutes. Filtration was performed through a glass tube filled with glass wool, and the obtained filtrate was subjected to ¹ H-NMR measurement. A peak derived from an oxymethylene group was confirmed at 3.2 to 3.7 ppm. The standard of chemical shift was the peak of tetramethylsilane.

[Comparative Example 1]
-Production of solid catalysts for olefin polymerization-
[First step]
A 100 ml four-necked flask fully purged with nitrogen was equipped with a stir bar, and this was dried at 200 ° C in a nitrogen atmosphere at 5.00 g of silica gel (trade name: H-122, manufactured by Asahi S-Tech Co., Ltd.), dehydrated toluene 44 ml was added and the temperature was raised to 50 ° C. by overheating in an oil bath. 2.5 ml of a toluene solution (1M) of triisobutylaluminum was added, and 19.0 ml of a toluene solution of methylaluminoxane (produced by Tosoh Finechem Co., Ltd., aluminum concentration 9.1% by weight) was further added. The mixture was reacted at 50 ° C. for 30 minutes, and further reacted at 95 ° C. for 4 hours. After standing at 60 ° C., 31 ml of the supernatant was removed by decantation to obtain a toluene slurry of silica-supported methylaluminoxane.

[Second step]
The toluene slurry of silica-supported methylaluminoxane obtained by the above method was kept at 35 ° C., and 20 ml of hexane was added thereto. After reacting for 45 minutes, diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (2,7-di-tert-butyl-fluorenyl), a transition metal compound, previously mixed A mixture of 150 mg of zirconium dichloride (produced by the method described in WO2004 / 087775), 1.86 ml of a toluene solution (1 M) of triisobutylaluminum and 4 ml of hexane was added. After reacting for 1 hour, the resulting slurry was filtered through a membrane filter. The obtained powder was dried under reduced pressure for 2 hours to obtain 9.16 g of powder. As a result of analysis, zirconium in the powder was 0.17% by weight. This was mixed with dehydrated liquid paraffin to make a 20.0 wt% slurry.

[Comparative Example 2]
-Homopolymerization of propylene (1)-
A magnetic stirrer was placed in a 50-ml branch flask thoroughly purged with nitrogen, to which 714 mg of the supported catalyst slurry prepared in Comparative Example 1 above, 1.0 mmol of triisobutylaluminum in hexane (Al = 1.0M) and dehydration were added. Hexane (5.0 ml) was added, and the mixture was introduced into a 2,000-ml SUS autoclave thoroughly purged with nitrogen. Thereafter, 500 g of liquid propylene was charged and polymerization was performed at 70 ° C. for 40 minutes, and then the polymerization was stopped by cooling the autoclave and purging propylene. The polymer was dried under reduced pressure at 80 ° C. for 10 hours.
The obtained polymer was 128.6 g of isotactic polypropylene, and the polymerization activity was 71.1 kg-PP / mmol-Zr · hr. As a result of polymer analysis, (η) = 3.29 dl / g, MFR = 0.27 g / 10 min, and the amount of coarse particles was 25.0 wt%. The bulk density could not be measured because the polymer powder was blocked in the funnel. The bulk density of the powder that passed through the sieve having an opening of 1 mm was 0.39 g / cm ³ . After polymerization, polymer adhesion was observed in the autoclave.

[Comparative Example 3]
-Homopolymerization of propylene (2)-
Polymerization was carried out under the same conditions as in Comparative Example 2 except that 308 mg of the supported catalyst slurry prepared in Comparative Example 1 was used, 500 g of liquid propylene was charged, and then 0.08 NL of hydrogen was added.
The obtained polymer was 143.8 g of isotactic polypropylene, and the polymerization activity was 184 kg-PP / mmol-Zr · hr. As a result of polymer analysis, (η) = 2.34 dl / g, MFR = 1.85 g / 10 minutes, and the amount of coarse particles was 50.3% by weight. The bulk density could not be measured because the polymer powder was blocked in the funnel. The bulk density of the powder that passed through a sieve having an opening of 1 mm was 0.36 g / cm ³ . After polymerization, polymer adhesion was observed in the autoclave.

[Comparative Example 4]
-Production of solid catalysts for olefin polymerization-
Preparation was carried out in the same manner as in Example 22 except that polyalkyleneoxy glycol (trade name: Adeka Pluronic L-71, manufactured by Asahi Denka Kogyo Co., Ltd.) was not added. As a result of analysis, the zirconium content in the supported catalyst was 0.19% by weight.

[Comparative Example 5]
-Ethylene slurry polymerization-
500 ml of heptane was charged into a SUS autoclave with an internal volume of 1,000 ml that had been sufficiently purged with nitrogen. Ethylene gas was circulated to saturate the autoclave with ethylene. To this, 0.25 mmol of hexane solution of triisobutylaluminum (Al = 0.5M) was added. On the other hand, polymerization was carried out in the same manner as in Example 23 except that 0.134 g of the slurry of the supported catalyst prepared in Comparative Example 4 was used in a 50 ml flask with a three-way cock and polymerization was carried out for 90 minutes. Polymer adhesion was observed on the inner wall of the polymerization vessel. The obtained polymer slurry was filtered with a Kiriyama funnel (φ95 mm, filter paper No. 5B). During the filtration, because of the fine powder, the filter paper was clogged and the filtration rate was slow. The polymer was dried under reduced pressure at 80 ° C. for 10 hours. The obtained polymer was 52.7 g, and the polymerization activity was 62.4 kg-PE / mmol-Zr · hr. As a result of polymer analysis, the bulk density was 0.38 g / cm ³ and the density was 930 kg / m ³ .

[Comparative Example 6]
-Propylene bulk polymerization-
Same as Example 4 except that 303 mg of the supported catalyst slurry prepared in Comparative Example 1 above was used, and a 10 g / L hexane solution of L-71 was charged into a 0.15 ml autoclave before charging the supported catalyst. Polymerization was performed under conditions. No adhesion was observed on the polymerization vessel. The obtained polymer was 92.6 g of isotactic polypropylene, and the polymerization activity was 120.7 kg-PP / mmol-Zr · hr. As a result of polymer analysis, the bulk density was 0.51 g / cm ³ and (η) = 2.46 dl / g. Although the fouling and the bulk density of the polymer were improved, the polymerization activity was lowered.

[Comparative Example 7]
-Ethylene gas phase polymerization-
500 g of sodium chloride was charged into a SUS autoclave with an internal volume of 1,000 ml that had been sufficiently purged with nitrogen. After sufficiently drying under heating, the mixture was cooled, ethylene gas was circulated, and the inside of the autoclave was saturated with ethylene. To this was added 0.25 mmol of triisobutylaluminum in hexane (Al = 0.5M). Meanwhile, 0.303 g of the slurry of the supported catalyst prepared in Comparative Example 4 and 0.13 mmol of a hexane solution of triisobutylaluminum (Al = 0.5M) were added to a 50 ml three-way cocked flask. The obtained catalyst slurry was charged into an autoclave. Thereafter, the inside of the autoclave was replaced with ethylene gas containing 4.0% by weight of 1-butene, and an ethylene / butene mixed gas was supplied at 80 ° C. so that the pressure became 0.8 MPa, and polymerization was performed for 60 minutes. The polymerization was stopped by cooling the autoclave and purging the residual gas. After 2 L of water was added to the obtained powder and stirred, the polymer slurry was exposed and filtered. After washing the polymer, it was dried under reduced pressure at 80 ° C. for 10 hours. The obtained polymer was 27.2 g, and the polymerization activity was 21.3 kg-PE / mmol-Zr · hr. As a result of polymer analysis, the amount of coarse particles was 2.2% by weight, the bulk density was 0.29 g / cm ³ , the density was 922 kg / m ³ , and (η) = 3.24 dl / g.

[Comparative Example 8]
-Production of solid catalysts for olefin polymerization-
Production was carried out in the same manner as in Example 27 except that polyalkyleneoxyglycol was not added to obtain a 10 wt% slurry of a solid catalyst. Zirconium in the powder was 0.19% by weight.

[Comparative Example 9]
Polymerization was carried out in the same manner as in Example 28 except that 601 mg of the solid catalyst slurry prepared in Comparative Example 8 was used. The obtained polymer was 172.5 g of isotactic polypropylene, and the polymerization activity was 210 kg-PP / mmol-Zr · hr. As a result of polymer analysis, MFR <0.01 g / 10 min, (η) = 6.93 dl / g, and the amount of coarse particles was 60.4% by weight. The bulk density could not be measured because the polymer powder was blocked in the funnel. The bulk density of the powder that passed through a sieve having an opening of 1 mm was 0.33 g / cm ³ . In addition, adhesion of the polymer was recognized in the autoclave.

[Comparative Example 10]
-Production of prepolymerization catalyst for olefin polymerization-
To the 200 mL flask, 10.01 g of liquid paraffin slurry prepared in Comparative Example 1 and 40 ml of hexane were added and heated to 34 ° C. To this, 2.0 ml of a 1 mol / L triisobutylaluminum hexane solution was added. Ethylene was blown into the gas phase at a rate of 1.5 NL / h, and polymerization was carried out at 35 ° C. for 4 hours. The residual ethylene was purged with nitrogen, and the resulting slurry was filtered through a membrane filter. Drying was performed under reduced pressure for 3 hours to obtain 6.70 g of a solid catalyst (K ′). 2.35 g of polymer was polymerized per 1 g of solid catalyst.

[Comparative Example 11]
-Contact treatment of prepolymerization catalyst for olefin polymerization and oxyalkylene skeleton-containing compound-
Under a dry nitrogen atmosphere, 2.0 g of the prepolymerized catalyst produced in Comparative Example 10 was weighed. To this, 13.2 g of dry hexane and 2.0 ml of a 20 g / L hexane solution of polyalkyleneoxyglycol (trade name: Adeka Pluronic L-71, manufactured by Asahi Denka Kogyo Co., Ltd.) were added and stirred at 35 ° C. for 4 hours. The resulting slurry was filtered using a Teflon (registered trademark) membrane filter having a pore size of 3 μm, and further washed 5 times with 10 ml of hexane. The resulting solid was dried under reduced pressure. The ignition loss of the obtained solid catalyst was 73.5% by weight. The obtained filtrate was concentrated under reduced pressure to obtain 38.2 mg of an oily substance. ^{From 1} H-NMR measurement, this oily product was polyalkyleneoxy glycol (trade name: Adeka Pluronic L-71, manufactured by Asahi Denka Kogyo Co., Ltd.). As a result of calculation from this result, the amount of polyalkyleneoxy glycol supported on the solid catalyst was 0.20% by weight.

[Comparative Example 12]
-Extraction test (1)-
In a dry nitrogen atmosphere, 500 mg of the solid material after contact treatment prepared in Comparative Example 11 was weighed. 7.5 g of dry hexane was added thereto, and the mixture was stirred for 1 hour in an atmosphere at 23 ° C. The obtained slurry was filtered using a Teflon (registered trademark) membrane filter having a pore diameter of 3 μm. The obtained filtrate was concentrated under reduced pressure, and dried under reduced pressure at 3 hPa for 3 hours in an atmosphere at 22 ° C. The obtained non-volatile component was less than 0.1 mg.

[Comparative Example 13]
−Extraction test (2) −
Under a dry nitrogen atmosphere, 160 mg of the solid material after contact treatment produced in Comparative Example 11 was weighed. This was left still in a desiccator equipped with a saturated aqueous potassium acetate solution and contacted with water vapor for 2 days. After removing from the desiccator, 1 g of deuterated acetonitrile was added in the atmosphere and stirred for 30 minutes. Filtration was performed through a glass tube filled with glass wool, and the obtained filtrate was subjected to ¹ H-NMR measurement. A peak derived from an oxymethylene group was confirmed at 3.2 to 3.7 ppm. The standard of chemical shift was the peak of tetramethylsilane.

[Comparative Example 14]
-Homopolymerization of propylene-
Polymerization was performed under the same conditions as in Example 18 except that 408 mg of the solid after contact treatment prepared in Comparative Example 11 was used as a catalyst. The obtained polymer was 144.5 g of isotactic polypropylene, and the polymerization activity was 99.7 kg-PP / mmol-Zr · hr. As a result of polymer analysis, MFR = 0.69 g / 10 min, (η) = 2.84 dl / g, bulk density was 0.32 g / cm ³ , and the amount of coarse particles was 1.9% by weight. In addition, adhesion of the polymer was recognized in the autoclave.

[Comparative Example 15]
-Homopolymerization of propylene-
Polymerization was performed under the same conditions as in Example 18 except that 400 mg of the solid material after contact treatment prepared in Comparative Example 11 was used as a catalyst. The obtained polymer was 144.5 g of isotactic polypropylene, and the polymerization activity was 69.1 kg-PP / mmol-Zr · hr. As a result of polymer analysis, MFR = 2.35 g / 10 min, (η) = 2.30 dl / g, bulk density was 0.51 g / cm ³ , and the amount of coarse particles was 0.0% by weight. A slight amount of polymer was observed in the autoclave. Fouling was not completely improved and the polymerization activity was significantly reduced.

  According to the present invention, an olefin polymer having excellent particle properties is efficiently produced without causing fouling. In particular, the effect is enormous in the production of a low-melting polymer, which has been difficult to produce industrially because fouling is likely to occur.

Claims (3)

Olefin polymerization characterized by comprising the metallocene compound represented by the following general formula (XIII), which satisfies the following requirements [1] and [2], and is produced by a method in which the following steps P1 and P2 are sequentially performed Propylene is selected from the group consisting of essential components and ethylene and an α-olefin having 4 to 10 carbon atoms in the presence of the solid catalyst (K) for use and, if necessary, (B) a group 13 element-containing compound of the periodic table The monomer (M) containing one or more of the above as an optional component is polymerized so that the repeating unit (U1) derived from propylene is selected from 50 to 100 mol%, ethylene and an α-olefin having 4 to 10 carbon atoms. The manufacturing method of the olefin polymer particle which contains the repeating unit (U2) of a olefin of a seed | species in the ratio of 0-50 mol%.

[1] The loss on ignition measured with a differential thermobalance is 30% by weight or less.
[2] A component having a molecular skeleton represented by the following general formula [I] is contained in the elution component to acetonitrile after contact with water vapor at room temperature and subsequent treatment with acetonitrile.

(In the above general formula [I], R represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.)

----- [XIII]

[Step P1] (A) An inorganic fine particle substantially composed of an atom selected from an aluminum atom, a silicon atom and an oxygen atom, and (B) a group 13 element-containing compound of the periodic table in a hydrocarbon medium The process of making it contact.
[Step P2] The suspension obtained in Step P1 above is brought into contact with (C) the oxyalkylene skeleton-containing compound, and (B) the group 13 element-containing compound in the periodic table and (D) metallocene, which have been contacted in advance. Adding and contacting the mixture with the compound.

The (B) group 13 element-containing compound of the periodic table is
(b-1) an organoaluminum compound represented by the following general formula [II],

(In the above general formula [II], R ¹ , R ² and R ³ may be the same or different from each other and each represents a group selected from a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms. .)
(b-2) an organoaluminum oxy compound, and
(b-3) organoboron compounds,
One or more compounds selected from

The (C) oxyalkylene skeleton-containing compound is
The polyoxyalkylene compound represented by the following general formula [VI], the following general formula
A polyoxyalkylene glycol represented by [VII], an aliphatic diethanolamide represented by the following general formula [VIII], or a tertiary amine compound represented by the following general formula [IX].

(In the above general formula [VI], R ^b is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and R ^a is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Selected from a group and an acyl group having 1 to 20 carbon atoms, k represents the average number of repeating units and is in the range of 1 to 100.)

(In the above general formula [VII], m, n and p represent the average number of repeating units, and m = 1 to 20, n = 2 to 50, and p = 1 to 20. Rc represents 1 to 20 carbon atoms. 10 alkyl groups)

(In the general formula [VIII], m is 1 to 30.)

(In the general formula [IX], R ^d is a hydrogen atom or a linear or branched alkyl group having 1 to 50 carbon atoms, and R ^e is a (CH ₂ ) _x OH group (wherein x is Which is an integer from 1 to 50). The method for producing olefin polymer particles according to claim 1, wherein the solid catalyst for olefin polymerization (K) satisfies the following requirement [3].
[3] The non-volatile component dissolved in the filtrate after separation of the solid portion after contact with hexane is 5% by weight or less of the weight of the solid catalyst for olefin polymerization (K).   The solid catalyst (K) for olefin polymerization is prepolymerized with at least one olefin selected from ethylene and an α-olefin having 3 to 8 carbon atoms, according to claim 1 or 2. A method for producing olefin polymer particles.

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